Key Engineering Materials Vols. 280-283

Abstract: Transition metal-doped TiO2 powders as a photocatalyst were prepared by sol-gel process and Sb, Bi and Nb were introduced into them as dopants. The photocatalytic behaviors of the doped TiO2 powder were studied as a function of dopant, doping concentration and preparation conditions. X-ray diffraction, FT-Raman, B.E.T. and scanning electron microscopy were applied for structural and microstructural studies. Optical properties of the doped TiO2 powders were studied by UV-Visible Spectrometer and photocatalytic activity of the doped TiO2 was characterized in terms of the degradation of 1,4-dichlorobenzene. X-ray difraction analysis showed that doping with a transition metal ion suppresses anatase-to-rutile phase transition compared with the pure TiO2. The Sb and Nb-doped TiO2 powders did not exhibit any other diffraction peaks except those belonging to TiO2. On the other hand, a diffraction peak of Bi4Ti3O12 appears for 5 at.% Bi-doped samples. All of the doped TiO2 powders had higher specific surface area than undoped TiO2. Surface area increased with increasing dopant concentration depending on the dopant, from 33.9 m2/g to 55.4m2/g. The UV-visible absorption spectra of doped samples were red-shifted by 20~50nm according to the doping level. Also transition metal doped TiO2 powders exhibited better photocatalytic activity than the undoped TiO2. The increase in photoactivity is probably due to the increase in the interfacial electron transfer, red shifts, and better crystallinity.

Abstract: Slim titanate naotubes was prepared from industrial coarse TiO2 powder by simple sonochemical-hydrothermal processing. The influences of ultrasonic irradiation on TiO2 precursors were investigated. The morphology and crystal structure of the products were characterized by TEM and X-ray diffraction, respectively. The typical products are long nanotubes around 8-10nm in out diameter. Both anatase and rutile TiO2 precursors can be transferred into titanate nanotubes in this sonochemical & hydrothermal processing.

Abstract: Nanometer cobalt oxide powders were obtained by decomposition of precursors CoC2O4×2H2O at 350°C for 3h. The precursors were synthesized by solid-state reaction with H2C2O4×2H2O and CoCO3 under microwave irradiation. The products were characterized by XRD and TEM. The results showed that the nanometer Co3O4 is cubic and the mean particle is 19 nm with narrow distribution and weak agglomeration.

Abstract: Ultrafine (Ba,Sr)TiO3-based powders used for making positive temperature coefficient of resistance (PTCR) were synthesized by two chemical steps: polyacrylamide gel process and liquid phase coating process. First, donor doped (Ba,Sr)TiO3 powders were synthesized by polyacrylamide gel process at rather low temperature, and the physical and chemical characteristics of the gels and the precursorpowders were investigated by DSC, TG, XRD and TEM. Secondly, acceptor and sintering aid were coated by an aqueous solution containing acceptor (Mn) and additive (Si). The characterization and sintering behavior of the semi-conducting powders and the PTC effect of ceramic samples prepared by the as-obtained powders were investigated.

Abstract: A sol-gel auto-ignited synthesis, which is a hybrid of sol-gel and auto-ignited techniques, was applied to preparation of homogeneous and stoichiometric BaCe0.8Y0.2O2.9 nanocrystalline ceramic powder as solid electrolyte used in solid oxide fuel cells at 1000°C. Optimal pH value for the mixed citrate-nitrate solutions was determined by calculation. The DTA-TG and XRD were used to investigate the thermal decomposition of the gel precursor. The structure and phase present of the nanocrystalline BaCe0.8Y0.2O2.9 powders were characterized by XRD, BET and SEM techniques.

Abstract: LiCoO2 spinel is one of the most promising cathode materials for Li-ion batteries. However, the capacity fading is aggravated at high voltage, resulting from cathode degradation and electrolyte decomposition owing to over-charging. To improve structural stability, surface modification is an effective method. In this study, nano-crystallized ZnO was coated on the surface of commercial LiCoO2 powders via sol-gel method. The correlation among the amount of coated ZnO, microstructure of modified cathode and the cycling behavior of surface-treated LiCoO2 powders is discussed. Moreover, the effects of cycling for cathodes with as-derived powders on the phase and morphology are also considered. The surface morphology observed from the scanning electron microscope (SEM) images shows that nano-crystallized and spherical ZnO particles with an average size of about 20 nm have developed after coating. The size of ZnO nanocrystallites is related to the initial concentration of Zn2+ cations. In comparing the characteristics of bare and coated LiCoO2 powders, improvement in cyceability of the ZnO-coated cathode is explored. It is confirmed that Zn2+ ions diffuse into the surface region of LiCoO2 particles. To reveal the effects of Zone coating on enhancing the electrochemical properties of LiCoO2 cathode during charge and discharge, the morphological differences between the cathode material before and after cycling are discussed.

Abstract: Surface modification on the electrode has a vital impact on lithium-ion batteries, and it is essential to probe the mechanism of the modified film on the surface of the electrode. In this study, a Li2O-2B2O3 film was coated on the surface of the cathode material by solution method. The cathode powders derived from co-precipitation method were calcined with various weight percent of the surface modified glass to form fine powder of single spinel phase with different particle size, size distribution and morphology. The thermogravimetry/differential thermal analysis was used to evaluate the appropriate heat treatment temperature. The structure was confirmed by the X-ray diffractometer along with the composition measured by the electron probe microanalyzer. From the field emission scanning electron microscope image and Laser Scattering measurements, the average particle size was in the range of 7-8µm. The electrochemical behavior of the cathode powder was examined by using two-electrode test cells consisted of a cathode, metallic lithium anode, and an electrolyte of 1M LiPF6. Cyclic charge/discharge testing of the coin cells, fabricated by both coated and un-coated cathode material, provided high discharge capacity. Furthermore, the coated cathode powder showed better cyclability than the un-coated one after the cyclic test. The introduction of the glass-coated cathode material revealed high discharge capacity and appreciably decreased the decay rate after cyclic test.

Abstract: The newly developed LiNi0.6Co0.4-xMnxO2 (0.1 < x < 0.3) cathode materials were synthesized by calcining the mixture of NixCoyMn1-x-y(OH)2 and Li2CO3 at 900-940 oC for 15 hr in flowing O2 atmosphere. The NixCoyMn1-x-y(OH)2 precursor was obtained by the chemical co-precipitation method at the pH value controlled by the concentration of NaOH, NH4OH and transition metal sulfate solution. The X-ray diffraction patterns indicated the pure layered hexagonal structure LiNi0.6Co0.4-xMnxO2. The electrochemical behavior of LiNixCoyMn1-x-yO2 powder was examined by using test cells cycled within the voltage range 3-4.3 V at the 0.1C rate for the first cycle and then at the 0.2C rate afterwards. LiNixCoyMn1-x-yO2 cathode materials showed good initial discharge capacity (165-180 mAh/g) and cycling performance. The fading rate was less than 5 % after 20 cycling test. It is demonstrated that LiNixCoyMn1-x-yO2 electrode should exhibit great potential for the future application in lithium-ion battery cathode material.

Abstract: Using citric acid (CA) as a chelating agent, (1-x)Ca0.4Sm0.4TiO3 –xLi0.5Nd0.5TiO3 (CSLNT) (x = 0.3) ceramic powders were synthesized by the Pechini method. The CSLNT precursor and derived oxide powders were characterized by differential thermal analysis, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy. Only perovskite CSLNT (x=0.3) phase appeared when the CSLNT precursor was calcined at 1050°C for 3 h. Compared with the conventional solid-state reaction method, microwave dielectric ceramics with better properties could be prepared by the Pechini method at lower sintering temperature.

Abstract: Powdery hausmannite (Mn3O4) is of interest in many industrial and technological applications. It is widely used as reactive catalysts, raw material of humidity sensors, and the cathode oxides of Li-ion secondary batteries. In this study, sub-micron and nano-meter sized Mn3O4 powders are prepared by an efficient method at room temperature. Mn(OH)2 nanocrystalsare commonly precipitated at first and then oxidized in the alkaline solution containing excess OH- anions. However, conventionally prepared Mn3O4 powders by the above process are ill-crystallized. To enhance the crystallinity of fabricated powders, CO3 2- anions are introduced into the process. The modified autoxidation method is practical to fabricate low-cost and high grade powders of Mn3O4. Advantages of the modified method are confirmed by both the electron micrographs and XRD patterns of synthesized powders. It is revealed that particle size of the products is in the sub-micron meter range, and the particle morphology can be adjusted by altering the precipitation sequence.